JP2002241568A - Thermoplastic resin composition and film or sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having excellent weatherability, flexibility, impact resistance, moldability and transparency, allowing controlling transparency if required and scarcely causing whitening or a change of transparency even at a low temperature and even when a deformation such as a tension or bending is applied, and a film or sheet given by forming the thermoplastic resin composition. SOLUTION: This thermoplastic resin composition comprises 5-95 wt.% of (A) a copolymer composed of an acrylic ester and a methacrylic ester and 95-5 wt.% of (B) a block copolymer comprising a methacrylic ester-based polymer block and an acrylic ester-based polymer bloc, where the block copolymer (B) is produced by a radical polymerization using a compound having thio- carbonyl-thio structure as a chain transfer agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to weather resistance, flexibility,
The present invention relates to a thermoplastic resin composition which is excellent in impact resistance, moldability, and transparency, can control transparency as required, and hardly causes cloudiness and change in transparency even when subjected to deformation such as tension or bending. In addition, the present invention has excellent weather resistance, flexibility, impact resistance, moldability, transparency, and can control the transparency as needed, and even if it undergoes deformation such as tension or bending, the opacity and change in transparency are reduced. The present invention relates to a film or a sheet formed of a thermoplastic resin composition which hardly occurs.

[0002]

2. Description of the Related Art Methacrylate resins have been used in various fields because of their excellent weather resistance and transparency. For example, it is formed into a film or a sheet, laminated with various materials such as resin, wood, and metal, and used for the purpose of preventing deterioration of a base material and maintaining aesthetic appearance. For the purpose of using as such a molded article, in order to improve moldability and impact resistance, a rubber component is dispersed in a methacrylate resin, or a graft copolymer having a rubber component is dispersed or grafted. Methods have been devised which use a mixture of a copolymer and a flexible polymer, or use the graft copolymer itself. In particular, as the graft copolymer, it is generally said that a core-shell particle type graft copolymer obtained by graft-polymerizing an outer layer portion called a shell on an inner layer portion called a core is effective, and a graft portion (shell portion) And a method in which the composition of a polymer other than the graft portion (shell portion) and the graft copolymer is changed stepwise to obtain a gradient polymer has been devised (Japanese Patent Publication No. 47-13371, Japanese Patent Publication No. Sho 47-13371). 50
-9022). Further, for the purpose of suppressing turbidity and change in transparency during deformation, a technology has been proposed in which the glass transition temperature (Tg) of the core portion (inner layer portion) of the core-shell particle type graft copolymer is 10 ° C. or more (Tokiko Shosho) 59-3664
No. 5, JP-B-59-36646).

[0003] However, these methods are insufficient in the effect of improving the impact resistance, and when the film is laminated on a substrate and used, the film itself breaks, or when the film or sheet is bent or pulled, it becomes white and cloudy. And the phenomenon that the transparency was reduced was observed. Such a phenomenon is particularly remarkable during deformation at a low temperature. If you try to solve these problems and increase the amount of flexible ingredients,
There was a problem that moldability and transparency were impaired.

[0004]

The problems to be solved by the present invention are excellent in weather resistance, flexibility, impact resistance, moldability and transparency, and the transparency can be controlled as required. It is also to provide a thermoplastic resin composition in which clouding and change in transparency are unlikely to occur even when a deformation such as tension or bending is applied, and by providing a film or sheet formed from such a thermoplastic resin composition. is there.

[0005]

Means for Solving the Problems The inventors of the present invention have studied to solve the above-mentioned problems, and have found that a copolymer (A) composed of an acrylate ester and a methacrylate ester has a content of 5 to 95% by weight and methacrylic acid. In a thermoplastic resin composition composed of 95 to 5% by weight of a block copolymer (B) containing an ester-based polymer block and an acrylate-based polymer block, the block copolymer (B) is converted to thiocarbonylthio. The present invention was found to be particularly effective when produced by radical polymerization by a reversible addition-elimination mechanism using a compound having a structure and a chain transfer constant of 0.1 or more as a chain transfer agent, and completed the present invention. Furthermore, the characteristics of the film or sheet formed from these thermoplastic resin compositions were also confirmed, and the present invention was completed.

That is, the present invention relates to the following invention.
(1) A block copolymer containing 5 to 95% by weight of a copolymer (A) composed of an acrylate and a methacrylate, and a methacrylate-based polymer block and an acrylate-based polymer block ( B) 95-
5% by weight of a thermoplastic resin composition, and
A thermoplastic resin composition (Claim 1), wherein the block copolymer (B) is produced by radical polymerization using a compound having a thiocarbonylthio structure as a chain transfer agent. 2.) The thermoplastic resin composition according to claim 1, wherein the copolymer (A) is a copolymer comprising butyl acrylate and methyl methacrylate (claim 2), (3). Block copolymer (B)
The thermoplastic resin according to claim 1 or 2, wherein the thermoplastic resin contains a polymer block containing 80% by weight or more of methyl methacrylate and a polymer block containing 80% by weight or more of butyl acrylate. A composition (claim 3);
(4) The copolymer (A) contains 50% by weight or more of a core-shell particle type graft copolymer (A-1) obtained by graft-polymerizing an outer layer portion called a shell on an inner layer portion called a core. The thermoplastic resin composition according to any one of claims 1 to 3 (claim 4), wherein the copolymer (A) is a core-shell particle type graft copolymer (A-
5) The thermoplastic resin composition according to claim 4, wherein the core portion in the core-shell particle type graft copolymer (A-1) is 90% by weight or more. The thermoplastic resin composition according to claim 4 or 5, wherein the weight average particle diameter of the thermoplastic resin composition is in the range of 30 to 200 nanometers (claim 6), (7) the copolymer (A) and the block. The thermoplastic resin composition according to any one of claims 1 to 6, wherein the thermoplastic resin composition (Claim 7) includes a vinyl polymer (C) as a component other than the copolymer (B).
(8) A film or sheet formed by molding the thermoplastic resin composition according to any one of claims 1 to 7 (claim 8).

[0007] Japanese Patent Application Laid-Open No. 2000-169659 discloses that
A graft copolymer containing a polymer component having a glass transition temperature of less than 25 ° C. and a polymer component having a glass transition temperature of 25 ° C. or more, and a block copolymer containing a methacrylic polymer and an acrylic polymer. Compositions are described. An acrylic graft copolymer is also disclosed as this graft copolymer. However, this publication does not disclose a block copolymer using the chain transfer agent of the present invention with respect to the block copolymer.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below, but the present invention is not limited to the following description.

The present invention relates to a copolymer (A) comprising an acrylate ester and a methacrylate ester in an amount of 5 to 95% by weight.
And a thermoplastic resin composition comprising 95 to 5% by weight of a block copolymer (B) containing a methacrylate-based polymer block and an acrylate-based polymer block, and such a thermoplastic resin composition The present invention relates to a film or sheet formed from a product.

The form of the copolymer (A) composed of an acrylate ester and a methacrylate ester used in the present invention includes a random copolymer, an alternating copolymer, and a comb-shaped graft copolymer containing a branch and a trunk. A polymer, a core-shell particle type graft copolymer (A-1) obtained by graft-polymerizing an outer layer part called a shell to an inner layer part called a core,
A copolymer obtained by multi-step addition polymerization of a methacrylate containing an acrylate in a core portion composed of an acrylate and a methacrylate, a mixture of an acrylate and a methacrylate, and a composition of both. Gradient copolymers obtained by additional polymerization while changing the ratio in multiple steps, and three-layer particle type graft copolymers having a central portion, an intermediate layer portion, and an outer layer portion, and the like can be given. These may be used alone or in combination of two or more.

The copolymer (A) preferably contains 50% by weight or more of the core-shell particle type graft copolymer (A-1) from the viewpoints of moldability, transparency and prevention of clouding during deformation. It is more preferable that the core-shell particle type graft copolymer (A-1) is contained in an amount of 90% by weight or more from the viewpoint of impact resistance. When the core-shell particle type graft copolymer (A-1) is used, the weight average particle diameter of the core portion is 30 to 30 from the viewpoint of moldability, prevention of white turbidity during deformation, and impact resistance.
Preferably it is in the range of 200 nanometers.

Examples of the acrylate used in the synthesis of the copolymer (A) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxy acrylate Butyl, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, stearyl acrylate, glycidyl acrylate, 2-acryloyloxypropyldimethoxymethylsilane, 2-acryloyloxypropyltrimethoxy Orchid, trifluoromethyl acrylate, pentafluoroethyl acrylate, 2,2,2-trifluoroethyl acrylate, 3-dimethylaminoethyl acrylate, isobutyl acrylate, 4-hydroxybutyl acrylate, t-butyl acrylate , Lauryl acrylate, alkyl-modified dipentaerythritol acrylate, ethylene oxide-modified bisphenol A diacrylate, carbitol acrylate, ε-caprolactone-modified dipentaerythritol acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, caprolactone-modified neopentyl hydroxypivalate Glycol ester diacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaery Thritol pentaacrylate, tetraethylene glycol acrylate, tetrahydrofurfuryl acrylate, tripropylene glycol acrylate, trimethylolpropane ethoxytriacrylate, trimethylolpropane triacrylate, neopentyl glycol diacrylate, neopentyl glycol hydroxypivalate diester Acrylate, 1,9-nonanediol acrylate, 1,4-butanediol acrylate, 2-propenoic acid [2- [1,1-dimethyl-2-[(1
-Oxo-2-propenyl) oxy] ethyl] -5-ethyl-1,3-dioxan-5-yl] methyl ester, 1,6-hexanediol acrylate, pentaerythritol triacrylate, 2-acryloyloxypropyl hydrogen Examples include, but are not limited to, phthalate, methyl 3-methoxyacrylate, allyl acrylate, and the like. These may be used alone or in combination of two or more. In terms of impact resistance, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-acrylate
-Butyl, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, alkyl acrylates such as dodecyl acrylate, and glycidyl acrylate are preferred. Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, etc. Alkyl acrylates having an alkyl group of 8 or less carbon atoms are more preferable, and methyl acrylate, ethyl acrylate, n-butyl acrylate,
Particularly preferred is t-butyl acrylate. For applications where oil resistance is required, 2-methoxyethyl acrylate,
3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate are preferred. When using a polyfunctional acrylate,
In order to suppress excessive crosslinking, the content is preferably within 10% by weight of the copolymer (A).

Examples of the methacrylate used in the synthesis of the copolymer (A) include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, and 2-butyl methacrylate. Ethylhexyl, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate , Tetrahydrofurfuryl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, dimethacrylic acid , 3-butylene glycol, trimethylolpropane trimethacrylate, isopropyl methacrylate, pentyl, hexyl methacrylate, heptyl methacrylate, octyl methacrylate,
Nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, toluyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-aminoethyl methacrylate, 2-methacryloyloxypropyl Trimethoxysilane, 2-methacryloyloxypolypyrdimethoxymethylsilane, trifluoromethyl methacrylate, pentafluoroethyl methacrylate,
Examples include, but are not limited to, 2,2,2-trifluoroethyl methacrylate. These may be used alone or in combination of two or more. In terms of impact resistance, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, tridecyl methacrylate, isopropyl methacrylate, pentyl methacrylate, methacrylic acid Hexyl, heptyl methacrylate, octyl methacrylate,
Nonyl methacrylate, decyl methacrylate, alkyl methacrylates such as decyl methacrylate, and glycidyl methacrylate are preferable, and methyl methacrylate, ethyl methacrylate, ethyl methacrylate, isopropyl methacrylate, and methacrylic acid are preferable in that an appropriate polymerization reaction rate is obtained. −
Alkyl methacrylates having an alkyl group having 8 or less carbon atoms, such as butyl, isobutyl methacrylate, t-butyl methacrylate, and 2-ethylhexyl methacrylate, are more preferable. Methyl methacrylate, methacrylic acid in terms of availability and price Ethyl, n-butyl methacrylate and t-butyl methacrylate are particularly preferred. For applications requiring oil resistance, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate are preferred. When a polyfunctional methacrylate is used, it is preferably within 10% by weight of the copolymer (A) in order to suppress excessive crosslinking.

The composition ratio of the acrylate ester and the methacrylate ester in the copolymer (A) is not particularly limited, and the glass transition temperature, refractive index, moldability, transparency, and resistance of the obtained copolymer (A) are not limited. What is necessary is just to determine from the balance of impact property, compatibility with a copolymer (B), etc. The combination of an acrylate and a methacrylate in the copolymer (A) is not particularly limited, but n-butyl acrylate / methyl methacrylate, t-butyl acrylate in terms of availability, ease of polymerization, and moldability. / Methyl methacrylate, ethyl acrylate / methyl methacrylate, ethyl acrylate / n-butyl acrylate / 2-methoxyethyl acrylate / methyl methacrylate, n-butyl acrylate / stearyl acrylate / methyl methacrylate, acrylic acid n-butyl / 2-hydroxyhexyl acrylate / methyl methacrylate, n-butyl acrylate / methyl methacrylate /
2-hydroxyhexyl methacrylate, n-acrylic acid
Butyl / methyl methacrylate / glycidyl methacrylate, ethyl acrylate / methyl methacrylate / glycidyl methacrylate, ethyl acrylate / n-butyl acrylate / 2-methoxyethyl acrylate / methyl methacrylate / glycidyl methacrylate, ethyl acrylate / T-butyl acrylate / 2-methoxyethyl acrylate /
Methyl methacrylate, t-butyl acrylate / stearyl acrylate / methyl methacrylate, t-butyl acrylate / 2-hydroxyhexyl acrylate / methyl methacrylate, t-butyl acrylate / methyl methacrylate / 2-hydroxy methacrylate Hexyl, acrylic acid t
-Butyl / methyl methacrylate / glycidyl methacrylate, ethyl acrylate / methyl methacrylate / glycidyl methacrylate, ethyl acrylate / t-butyl acrylate / 2-methoxyethyl acrylate / methyl methacrylate / glycidyl methacrylate, etc. are preferred. In view of cost, n-butyl acrylate / methyl methacrylate is more preferable.

As the copolymer (A), the above-mentioned copolymer may be used alone, a plurality of copolymers may be mixed and used, or the homopolymer may be used as a component other than the copolymer. May be included.

Glass transition temperature (Tg) of copolymer (A)
Is not particularly limited, but from the viewpoint of moldability, flexibility and impact resistance of the obtained thermoplastic resin composition, the temperature is from 0 ° C to 20 ° C.
It is preferably in the range of 0 ° C, 20 ° C to 150 ° C
More preferably in the range of 40 ° C to 100 ° C.
It is particularly preferable that it is in the range of

When the copolymer (A) contains the core-shell particle type graft copolymer (A-1), the ratio of the core to the shell in the core-shell particle type graft copolymer (A-1) is not particularly limited. However, the proportion of the core is preferably from 10 to 80% by weight, more preferably from 20 to 70% by weight. If the core in the core-shell particle type graft copolymer (A-1) is less than 10% by weight, the impact resistance may be low. May worsen.

Core-shell particle type graft copolymer (A-
The components of the core and the shell in 1) are not particularly limited, and any acrylate and methacrylate that can be used in the synthesis of the copolymer (A) can be used. However, in terms of impact resistance and moldability of the obtained thermoplastic resin composition, the glass transition temperature (Tg) of either the core or the shell is required.
Is less than 25 ° C., the other glass transition temperature (Tg) is preferably 25 ° C. or more, and the glass transition temperature (Tg) of either the core or the shell is less than 0 ° C., and the other glass More preferably, the dislocation temperature (Tg) is 30 ° C. or higher. Further, in terms of moldability and flexibility of the thermoplastic resin composition, the glass transition temperature of the core (Tg)
Is preferably lower than the glass transition temperature (Tg) of the shell.

The core-shell particle type graft copolymer (A-
In the synthesis of 1), a polyfunctional compound having two or more ethylenically unsaturated groups having radical (co) polymerizability may be used as a crosslinking component. Such polyfunctional compounds include ethylene glycol di (meth) acrylate,
Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetra or higher polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tri or higher polypropylene glycol di (Meth) acrylate, 1,
3-butylene glycol di (meth) acrylate, 1,
4-butanediol di (meth) acrylate, glycerin di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate,
Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, hydroxyisocyanurate tri (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-
Hexanediol di (meth) acrylate, glycerol allyloxydi (meth) acrylate, 1,1,1-tris (hydroxymethyl) ethanedi (meth) acrylate, 1,1,1-tris (hydroxymethyl) ethanetri (meth) acrylate (Meth) acryloyl group-containing compounds such as di (meth) acrylate of bismethacrylamide and bisphenol A polyalkylene glycol adducts; vinyl group-containing compounds such as divinylbenzene and divinyl adipate; diallyl phthalate, diallyl maleate, allyl (meta) ) Allyl group-containing compounds such as acrylate, triallyl cyanurate and triallyl isocyanurate are exemplified, but not limited thereto. These may be used alone or in combination of two or more. Among these polyfunctional compounds, a (meth) acryloyl group-containing compound is preferable in terms of efficient polymerization. When these polyfunctional compounds are used for the synthesis of the core-shell particle type graft copolymer (A-1), the amount of the polyfunctional compound used is the core-shell particle type graft copolymer (A-1).
0.1-20 weight% of the inside is preferable, and 0.5-10 weight% is more preferable. When the amount is less than 0.1% by weight, transparency may be deteriorated, and when it exceeds 20% by weight, impact resistance may be reduced.

The core-shell particle type graft copolymer (A-
The weight average particle diameter of the core in 1) is not particularly limited, but is preferably 10 to 500 nm, and 20 to 30 nm.
0 nm is more preferable, and 30 to 200 nm is particularly preferable. If the weight average particle diameter of the core is less than 10 nanometers, the impact resistance of the thermoplastic resin composition may be low, and if it exceeds 500 nanometers, the moldability and transparency may be poor.

The method for producing the copolymer (A) is not particularly limited, and it can be carried out by various conventionally known methods such as a solution polymerization method, an emulsion polymerization method, a suspension polymerization method and a bulk polymerization method. In the production of the copolymer (A), a polymerization initiator is used. Examples of such a polymerization initiator include cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, and , 1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane,
1,1-bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydro Peroxide, 1,3-bis (tert-butylperoxy) -m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, tert
-Butylcumyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide,
Peroxide-based polymerization initiators such as bis (tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxybenzoate, and 2,5-dimethyl-2,5-di (benzoylperoxy) hexane;
'-Azobis (isobutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), azocumene, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobisdimethylvalero Nitrile,
4,4′-azobis (4-cyanovaleric acid), 2- (te
rt-butylazo) -2-cyanopropane, 2,2'-
Azobis (2,4,4-trimethylpentane), 2,
2'-azobis (2-methylpropane), dimethyl 2,
Azo-based polymerization initiators such as 2′-azobis (2-methylpropionate); potassium persulfate, sodium persulfate,
Inorganic peroxides such as ammonium persulfate; monomers that generate radical species thermally, such as styrene; compounds that generate radical species by light, such as benzoin derivatives, benzophenones, acylphosphine oxides, and photoredox systems; Sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, ferrous sulfate etc. as reducing agents,
Examples include, but are not limited to, redox-type polymerization initiators using oxidizing agents such as potassium peroxodisulfate, hydrogen peroxide, and t-butyl hydroperoxide. These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator to be used is not particularly limited. However, from the viewpoint of the polymerization rate and the control of the polymerization, 0.1 to 2 parts by weight per 100 parts by weight of the monomer component is used.
0 parts by weight is preferable, and 0.5 to 10 parts by weight is more preferable. It is also possible to use a polymerization initiation system by electron beam irradiation, X-ray irradiation, radiation irradiation or the like. Regarding such a polymerization initiation method, see Mod and S.
olomon "The Chemistry of F
ree Radical Polymerizatio
n ", Pergamon, London, 1995, 5
The method described on page 3-95 can be used.

When the copolymer (A) is synthesized in an organic solvent, examples of the organic solvent used include hydrocarbon solvents such as heptane, octane and mineral spirit; ethyl acetate, n-butyl acetate, and isobutyl acetate. Ester solvents such as ethylene glycol monomethyl ether acetate and diethylene glycol monobutyl ether acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and cyclohexanone; methanol, ethanol, isopropanol, n-butanol, sec-butanol, isobutanol and the like Alcohol solvents such as n-butyl ether, dioxane, ethylene glycol dimethyl ether and ethylene glycol diethyl ether; toluene, xylene , SWASOL 310 (manufactured by Cosmo Oil Co., Ltd.), SWASOL 1000 (manufactured by Cosmo Oil Co., Ltd.), SWASOL 1500 (manufactured by Cosmo Oil Co., Ltd.), and the like, but not limited thereto. . These may be used alone or in combination of two or more.

When the copolymer (A) is synthesized by the emulsion polymerization method, the emulsifier to be used is not particularly limited, and fatty acid soap, rosin acid soap, sodium naphthalenesulfonate formalin condensate, sodium alkylbenzenesulfonate, Anionic surfactants such as ammonium alkyl sulfate, triethanolamine alkyl sulfate, sodium dialkyl sulfosuccinate, sodium alkyl diphenyl ether disulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate; polyoxyethylene alkyl ether , Polyoxyethylene higher alcohol ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene Rubitoru fatty acid ester,
Examples include nonionic surfactants such as glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, and alkyl alkanolamide; and cationic surfactants such as alkyltrimethylammonium chloride. These emulsifiers may be used alone or in combination of two or more. If necessary, a cationic surfactant such as an alkylamine hydrochloride may be used. The amount of the emulsifier is not particularly limited, but is usually 1 to 10 parts by weight based on 100 parts by weight of the monomer.

When the synthesis of the copolymer (A) is carried out by a suspension polymerization method, the dispersant used is not particularly limited, and for example, partially saponified polyvinyl acetate, polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, gelatin, polydisperse, etc. Conventionally known compounds such as an alkylene oxide, a combination of an anionic surfactant and a dispersing aid can be used. These may be used alone or in combination of two or more. The amount of the dispersant is not particularly limited, but is usually 1 to 100 parts by weight of the monomer.
10 parts by weight.

In the production of the copolymer (A), the oxygen concentration in the reaction system is preferably 10000 ppm or less, more preferably 5000 ppm or less, and more preferably 1000 ppm or less in terms of high reactivity. Is particularly preferred. For this reason, it is preferable to carry out the reaction in an atmosphere of an inert gas such as nitrogen, argon or helium.

The block copolymer (B) used in the present invention comprises a methacrylate polymer block and an acrylate polymer block.
Here, the methacrylate polymer block is
It is a polymer block containing at least 50% by weight of a methacrylate, and an acrylate-based polymer block is a polymer block containing at least 50% by weight of an acrylate. As the structure of the block copolymer (B), an AB type diblock copolymer and an ABA type triblock copolymer are preferable in that the moldability of the obtained thermoplastic resin composition is good. , And (AB) n-type multiblock copolymers are preferred. In the block copolymer (B), the composition ratio (monomer molar ratio) of the methacrylate ester polymer block to the acrylate ester polymer block is (methacrylate ester polymer block) in terms of processability and flexibility. ): (Acrylate polymer block) = 5: 95 to 90:10 is preferred,
10: 90-80: 20 is more preferable, and 20: 80-
70:30 is particularly preferred. Further, the block copolymer (B) may contain a graft structure or a branched structure. The number average molecular weight of the block copolymer (B) is not particularly limited, but is preferably from 20,000 to 500,000, more preferably from 30,000 to 400,000 in view of processability. In the block copolymer (B), in terms of moldability and heat resistance, the glass transition temperature (Tg) of the polymer block portion containing a methacrylate ester as a main component is preferably 25 ° C. or higher, more preferably 40 ° C. or higher. . In the block copolymer (B), the glass transition temperature (T
g) is preferably 25 ° C. or lower, more preferably 0 ° C. or lower, and particularly preferably −20 ° C. or lower.

In the block copolymer (B), the methacrylate ester polymer block is composed of at least 50% by weight of a methacrylate ester and a vinyl monomer component copolymerizable therewith. Examples of such methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, and methacrylic acid 2
-Ethylhexyl, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methacrylic acid Glycidyl,
Tetrahydrofurfuryl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane trimethacrylate, isopropyl methacrylate, pentyl methacrylate , Hexyl methacrylate,
Heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, toluyl methacrylate,
Isobornyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-aminoethyl methacrylate, 2-methacryloyloxypropyltrimethoxysilane, 2-methacryloyloxypolypyrdimethoxymethylsilane, trifluoromethyl methacrylate, Examples include, but are not limited to, pentafluoroethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and the like. These may be used alone or in combination of two or more. Of these, methyl methacrylate is preferred because of its good availability, moldability, workability, and heat resistance. Examples of the vinyl monomer copolymerizable therewith include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate,
Hexyl acrylate, 2-ethylhexyl acrylate,
Cyclohexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-methoxy acrylate Hydroxyethyl, 2-hydroxypropyl acrylate, stearyl acrylate, glycidyl acrylate, 2-acryloyloxypropyldimethoxymethylsilane, 2-acryloyloxypropyltrimethoxysilane, trifluoromethyl acrylate, pentafluoroethyl acrylate, acrylic acid 2,2,2-trifluoroethyl, 3-dimethylaminoethyl acrylate, isobutyl acrylate, 4-hydroxybutyl acrylate, t-acrylate
Butyl, lauryl acrylate, alkyl-modified dipentaerythritol acrylate, ethylene oxide-modified bisphenol A diacrylate, carbitol acrylate, ε-caprolactone-modified dipentaerythritol acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, caprolactone-modified neohydroxypivalate Pentyl glycol ester diacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, tetraethylene glycol acrylate, tetrahydrofurfuryl acrylate, tripropylene glycol acrylate, trimethylolpropane ethoxy triacrylate, trimethyl Methylol propane triac Rate, neopentyl glycol diacrylate, neopentyl glycol hydroxypivalic acid ester diacrylate, acrylic acid 1,9
Nonanediol, 1,4-butanediol acrylate,
2-propenoic acid [2- [1,1-dimethyl-2-[(1-oxo-2-propenyl) oxy] ethyl] -5-ethyl-1,3-dioxan-5-yl] methyl ester, 1,6-hexanediol acrylate,
Acrylates such as pentaerythritol triacrylate, 2-acryloyloxypropyl hydrogen phthalate, methyl 3-methoxyacrylate, allyl acrylate; styrene, α-methylstyrene, p-
Aromatic alkenyl compounds such as methylstyrene, p-methoxystyrene, divinylbenzene and vinylnaphthalene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; conjugated diene compounds such as butadiene and isoprene; vinyl chloride, vinylidene chloride and tetrafluorocarbon Halogen-containing unsaturated compounds such as ethylene, hexafluoropropylene, vinylidene fluoride and chloroprene; silicon-containing unsaturated compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, maleic monoester, maleic acid Unsaturated dicarboxylic acid compounds such as diester, fumaric acid, fumaric acid monoester, and fumaric acid diester; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, cinnamate Vinyl ester compounds such as maleimide; maleimide compounds such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; and acrylic acid and methacrylic acid. Examples include, but are not limited to: These may be used alone or in combination of two or more. As the methacrylic acid ester-based polymer block in the block copolymer (B), the thermoplastic resin composition to be obtained and the flexibility of the film or sheet formed from the same are suppressed in that cloudiness and change in transparency during deformation are suppressed. , Methyl methacrylate to 8
It is preferred that the content be 0% by weight or more.

In the block copolymer (B), the acrylate polymer block is composed of at least 50% by weight of an acrylate ester and a vinyl monomer component copolymerizable therewith. Such acrylates include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, acrylic Octyl acid, decyl acrylate, dodecyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, acrylic acid 2-hydroxypropyl, stearyl acrylate, glycidyl acrylate, 2-acryloyloxypropyldimethoxymethylsilane, 2-acryloyloxypropyltrimethoxysilane, trifluoroacrylate Chill, pentafluoroethyl acrylate, 2 acrylate,
2,2-trifluoroethyl, 3-dimethylaminoethyl acrylate, isobutyl acrylate, 4-acrylic acid
Hydroxybutyl, t-butyl acrylate, lauryl acrylate, alkyl-modified dipentaerythritol acrylate, ethylene oxide-modified bisphenol A diacrylate, carbitol acrylate, ε-caprolactone-modified dipentaerythritol acrylate, caprolactone-modified tetrahydrofurfuryl acrylate , Caprolactone-modified neopentyl glycol hydroxypivalate diacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, tetraethylene glycol acrylate, tetrahydrofurfuryl acrylate, tripropylene glycol acrylate, tri Methylol propane ethoxy triacrylate Trimethylolpropane triacrylate, neopentyl glycol diacrylate,
Neopentyl glycol hydroxypivalate diacrylate, 1,9-nonanediol acrylate,
1,4-butanediol acrylate, 2-propenoic acid [2- [1,1-dimethyl-2-[(1-oxo-2-propenyl) oxy] ethyl] -5-ethyl-1,3- Dioxan-5-yl] methyl ester, 1,6-hexanediol acrylate, pentaerythritol triacrylate, 2-acryloyloxypropyl hydrogen phthalate, methyl 3-methoxyacrylate, allyl acrylate, and the like. It is not limited. These may be used alone or in combination of two or more. Of these, butyl acrylate is preferred because of its good availability, flexibility, and impact resistance. Examples of the vinyl monomer copolymerizable therewith include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, methacrylic acid 2
-Ethylhexyl, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methacrylic acid Glycidyl,
Tetrahydrofurfuryl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane trimethacrylate, isopropyl methacrylate, pentyl methacrylate , Hexyl methacrylate,
Heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, toluyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxyethyl methacrylate Butyl, 2-aminoethyl methacrylate, 2-methacryloyloxypropyltrimethoxysilane, 2-methacryloyloxypolypyrdimethoxymethylsilane, trifluoromethyl methacrylate, pentafluoroethyl methacrylate, 2,2,2 methacrylate
Methacrylates such as trifluoroethyl; styrene, α-methylstyrene, p-methylstyrene, p
-Aromatic alkenyl compounds such as methoxystyrene, divinylbenzene and vinylnaphthalene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile;
Conjugated diene compounds such as butadiene and isoprene; vinyl chloride, vinylidene chloride, tetrafluoroethylene,
Halogen-containing unsaturated compounds such as hexafluoropropylene, vinylidene fluoride and chloroprene; silicon-containing unsaturated compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, maleic monoester, maleic diester; Unsaturated dicarboxylic acid compounds such as fumaric acid, fumaric acid monoester and fumaric acid diester; vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; maleimide, methylmaleimide, ethyl Maleimide compounds such as maleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide Acrylic acid, and the like methacrylic acid, but is not limited thereto. These may be used alone or in combination of two or more. As the acrylate polymer block in the block copolymer (B), flexibility of the obtained thermoplastic resin composition and a film or sheet obtained by molding the same, suppression of cloudiness and change in transparency upon deformation are suppressed. , N-butyl acrylate, isobutyl acrylate and t-butyl acrylate are preferred, n-butyl acrylate is more preferred, and it is particularly preferred to contain 80% by weight or more of n-butyl acrylate.

In the present invention, as a method for producing the block copolymer (B), a radical polymerization method using a compound having a thiocarbonylthio structure as a chain transfer agent is applied. The chain transfer constant of the chain transfer agent is preferably 0.1 or more. In this polymerization, it is presumed that radical polymerization by a reversible addition-elimination mechanism is in progress. Regarding radical polymerization by such a reversible non-elimination mechanism, see International Patent WO
98/01478, International Patent WO99 / 05099, International Patent WO99 / 31144, Macromoleccu
Les 1998 Vol. 31, No. 16, pp. 5559-5562, Macromolecules 1999 Vol. 32, No. 6
No. 2071-2074, Polym. Prep
r. 1999 Vol. 40, No. 2, pp. 342-343, Po
lym. Prepr. 1999 Vol. 40 No. 2 397-3
98 pages, Polym. Prepr. 1999 40
Vol. 2, pp. 899-900, Polym. Prep
r. Vol. 40, No. 2, 1999, pp. 1108-1081,
Macromolecules 1999 Vol. 32, No. 21, pp. 6977-6980, Macromolecules
es 2000 Vol. 33, No. 2, pp. 243-245, Ma
cromol. Symp. 2000, Volume 150, 33-3
It is described on page 8 and the like. As the compound having a thiocarbonylthio structure used as a chain transfer agent in the present invention, the compounds described in the above-mentioned documents can be used, and have a structure represented by the general formula (1) in the molecule.

[0030]

Embedded image Examples of such compounds include those represented by the general formula (2)

[0031]

Embedded image (In the formula, R ¹ is a monovalent organic group having 1 or more carbon atoms, and may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and the like. Z ¹ is a hydrogen atom; a halogen atom Or a monovalent organic group, a nitrogen atom, an oxygen atom,
It may contain a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom and the like. ), General formula (3)

[0032]

Embedded image (Wherein R ² and R ³ are monovalent organic groups having 1 or more carbon atoms, and include a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom,
It may contain a silicon atom, a phosphorus atom, etc., and may be the same or different. Z ² is a divalent organic group, which may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, and the like. ), General formula (4)

[0033]

Embedded image (Wherein R ⁴ and R ⁵ are monovalent organic groups having 1 or more carbon atoms, and include a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom,
It may contain a silicon atom or the like, and may be the same or different. ), General formula (5)

[0034]

Embedded image (Wherein, R ⁶ is a divalent organic group having 1 or more carbon atoms, and may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and the like. Z ³ and Z ⁴ represent a hydrogen atom A halogen atom; or a monovalent organic group, which may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom, etc., and may be the same or different from each other); Equation (6)

[0035]

Embedded image (In the formula, R ⁷ is a divalent organic group having 3 or more carbon atoms, and may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, etc.), and the general formula (7)

[0036]

Embedded image (In the formula, R ⁸ is a divalent organic group having 1 or more carbon atoms, and may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, and the like. Z ⁵ is a divalent organic group. And
It may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom and the like. ), General formula (8)

[0037]

Embedded image (In the formula, R ⁹ is a divalent organic group having 3 or more carbon atoms and may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, etc.), and the general formula (9)

[0038]

Embedded image (Wherein, R ¹⁰ is a monovalent organic group having 1 or more carbon atoms, and may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, etc. Z ⁶ is an a-valent organic group) And
It may contain a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom, a silicon atom, a phosphorus atom and the like. a is an integer of 3 or more. ) And the like, but are not limited thereto. Specific examples of these compounds having a thiocarbonylthio structure include compounds represented by general formula (10)

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image (In the formula, Me represents a methyl group, Et represents an ethyl group, Ph represents a phenyl group, and r is an integer of 1 or more.).

Among these compounds having a thiocarbonylthio structure, compounds having a chain transfer constant of 0.1 or more can be suitably used in the present invention. The chain transfer constant is described in the above literature, and in the literature cited in the literature, but from the viewpoint of obtaining a polymer having a smaller molecular weight distribution, the chain transfer constant is preferably 1 or more, More preferably, it is 10 or more.

In performing radical polymerization using such a compound having a thiocarbonylthio structure as a chain transfer agent, there is no particular limitation on the polymerization method.
Applicable to emulsion polymerization, suspension polymerization, bulk polymerization, etc.
It is only necessary to add a compound having a thiocarbonyl structure to these polymerization reaction systems. The embodiment of the polymerization is not particularly limited, and a conventionally known method such as a batch method, a continuous method, and a sequential addition method can be widely applied. The amount of the chain transfer agent having a thiocarbonylthio structure is not particularly limited, but the degree of polymerization and the number average molecular weight of the polymer can be controlled by adjusting the molar ratio with the monomer. For example, when synthesizing a polymer having a degree of polymerization of 1,000, the chain transfer agent is added so that the content of the dithiocarbonylthio structure becomes 1/1000 equivalent to the monomer. There is no particular limitation on the timing of addition of the chain transfer agent having a thiocarbonylthio structure, and the chain transfer agent may be charged in the reaction vessel before the start of polymerization, may be introduced into the reaction vessel at the start of polymerization, or may be added during the polymerization. It may be introduced into the reaction vessel. Among various addition methods, from the viewpoint that a polymer having a small molecular weight distribution can be obtained, a method of charging the reaction vessel before the start of polymerization or a method of introducing it into the reaction vessel at the start of polymerization is preferable. Is more preferable.

In the production of the block copolymer (B),
A block copolymer may be formed by a method of sequentially adding different monomers. Alternatively, after each block portion is separately polymerized, different blocks may be bonded to each other by a chemical reaction to form a block copolymer. For example, when preparing a block copolymer of methyl methacrylate and n-butyl acrylate, first, methyl methacrylate is polymerized by radical polymerization using a compound having a thiocarbonylthio structure as a chain transfer agent, and then the reaction is performed. A method of polymerizing n-butyl acrylate from the terminal of polymethyl methacrylate by introducing n-butyl acrylate into a vessel; by radical polymerization using a compound having a thiocarbonylthio structure as a chain transfer agent,
First, methyl methacrylate is polymerized, and the obtained polymethyl methacrylate is once taken out and purified, and then the polymethyl methacrylate is again charged into a reactor together with a polymerization initiator and the like, and n-butyl acrylate is introduced to introduce poly (methyl methacrylate) into the reactor. A method of polymerizing n-butyl acrylate from the terminal of methyl methacrylate; a method of further bonding the block copolymer of methyl methacrylate and n-butyl acrylate obtained by any of the above methods by a chemical reaction; Polymethyl methacrylate polymerized by radical polymerization using a compound having a carbonylthio structure as a chain transfer agent, and similarly separately polymerized poly (n-butyl acrylate) may be bonded by a chemical reaction. The monomers used are not limited to these. Not shall.

The method for bonding a polymer obtained by radical polymerization using a compound having a thiocarbonylthio structure as a chain transfer agent by a chemical reaction is not particularly limited. For example, a polymerization initiator having a reactive functional group may be used. After polymerization using a reactive functional group (a reaction between a hydroxyl group and an isocyanate group; a reaction between an amino group and an isocyanate group; a reaction between a hydroxyl group and a carboxyl group; a reaction between an amino group and a carboxyl group; Coupling between isocyanate groups; coupling between hydroxyl groups; coupling between carboxyl groups; reaction between unsaturated groups and hydrosilyl groups; coupling between silanols; coupling between alkoxysilyl groups; Reaction of halides; organometallic reagents such as Grignard reaction Reaction used: Diels-Alder reaction; Mannich reaction: Friedel-Crafts reaction; reaction of hydroxyl group with epoxy group, etc.); after polymerization using a compound having a reactive functional group as a chain transfer agent having a thiocarbonylthio structure, Method of bonding using a functional group (reaction between hydroxyl group and isocyanate group; reaction between amino group and isocyanate group; reaction between hydroxyl group and carboxyl group; reaction between amino group and carboxyl group; reaction between hydroxyl group and urethane bond; isocyanate group Coupling;
Coupling between hydroxyl groups; coupling between carboxyl groups; reaction between unsaturated groups and hydrosilyl groups; coupling between silanols; coupling between alkoxysilyl groups; reaction between alcoholates and halides; Reactions to be used: Diels-Alder reaction; Mannich reaction: Friedel-Crafts reaction; reaction between hydroxyl group and epoxy group, etc.); Method of bonding using a thiocarbonylthio group present at the terminal of the polymer (a thiocarbonylthio group is converted to a primary amine) A method of reacting a compound, a secondary amine compound, or a basic compound to form a mercapto group, and coupling the mercapto groups with each other in the presence of a catalyst such as lead oxide; a method of reacting the mercapto group with an isocyanate group; One to react with epoxy group A method of reacting the mercapto group with a carboxyl group; a method of converting the mercapto group into a thioalcoholate and reacting with a halide; a method of coupling the mercapto group with a hydroxyl group; a reaction of adding the mercapto group to an unsaturated group; A method of reacting the mercapto group with a urethane bond; a method of reacting the mercapto group with a urea bond;
Or more metal ions (Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺
And the like) can be used. These methods may be performed alone or in combination. Further, regarding the reaction for converting these thiocarbonylthio structures,
The present invention is applicable to reactions other than the reaction for the purpose of coupling between polymers. For example, by converting a thiocarbonylthio group into a mercapto group, or by reacting with a hydrogen atom by reacting a trialkyltin hydride or the like in the presence of a polymerization initiator, heat resistance is improved, and coloring and discoloration are improved. It may be suppressed.

Examples of the polymerization initiator used in the production of the block copolymer (B) include, for example, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, 1,1-bis (tert) -Butyl peroxy)
-3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, n
-Butyl-4,4-bis (tert-butylperoxy) valerate, cumene hydroperoxide, 2,
5-dimethylhexane-2,5-dihydroperoxide, 1,3-bis (tert-butylperoxy)-
m-isopropyl) benzene, 2,5-dimethyl-2,
5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, tert-butylcumyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide,
2,4-dichlorobenzoyl peroxide, bis (t
tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxybenzoate, 2,
Peroxide-based polymerization initiators such as 5-dimethyl-2,5-di (benzoylperoxy) hexane; 2,2′-azobis (isobutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile) ), Azocumene, 2,
2'-azobis (2-methylbutyronitrile), 2,2
'-Azobisdimethylvaleronitrile, 4,4'-azobis (4-cyanovaleric acid), 2- (tert-butylazo) -2-cyanopropane, 2,2'-azobis (2,
Azo-based polymerization initiators such as 4,4-trimethylpentane), 2,2′-azobis (2-methylpropane) and dimethyl 2,2′-azobis (2-methylpropionate); potassium persulfate, persulfate Inorganic peroxides such as sodium; monomers that generate radical species thermally, such as styrene; compounds that generate radical species by light, such as benzoin derivatives, benzophenones, acylphosphine oxides, and photoredox systems; sulfurous acid Redox polymerization using sodium, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, ferrous sulfate, etc. as reducing agents, and potassium peroxodisulfate, hydrogen peroxide, t-butyl hydroperoxide, etc. as oxidizing agents Examples of the initiator include, but are not limited to, Not to. These polymerization initiators may be used alone or in combination of two or more. It is also possible to use a polymerization initiation system by electron beam irradiation, X-ray irradiation, radiation irradiation or the like. Regarding such a polymerization initiation method, see Mod and S.
olomon "The Chemistry of F
ree RadicalPolymerizatio
n ", Pergamon, London, 1995, 5
The method described on page 3-95 can be used.

The amount of the polymerization initiator used in the production of the block copolymer (B) is not particularly limited. And less than 1 equivalent of the amount of the chain transfer agent having a thiocarbonylthio structure.
5 equivalents or less are more preferable, and 0.2 equivalents or less are particularly preferable. In addition, in order to control the amount of radical species generated during polymerization, in conjunction with the amount of polymerization initiator used, in the case of a thermally dissociated polymerization initiator, the temperature is adjusted, or light or an electron beam is used. In the case of a polymerization initiator that generates a radical, it is preferable to adjust the amount of energy to be irradiated.

When the block copolymer (B) is produced in an organic solvent, examples of the organic solvent used include hydrocarbon solvents such as heptane, octane, and mineral spirit; ethyl acetate, n-butyl acetate, and acetic acid. Isobutyl,
Ester solvents such as ethylene glycol monomethyl ether acetate and diethylene glycol monobutyl ether acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and cyclohexanone; methanol and ethanol, isopropanol, n-butanol, sec-butanol and isobutanol Alcohol solvents; ether solvents such as n-butyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether; toluene, xylene, swazol 310 (manufactured by Cosmo Oil), swazol 1000 (manufactured by Cosmo Oil), swazol 1500 (cosmo) Petroleum-based solvents), but are not limited thereto. . These may be used alone or in combination of two or more.

When the production of the block copolymer (B) is carried out by an emulsion polymerization method, the emulsifier to be used is not particularly limited, and fatty acid soap, rosin acid soap, sodium naphthalenesulfonate formalin condensate, sodium alkylbenzenesulfonate are used. Anionic surfactants such as ammonium alkyl sulfate, triethanolamine alkyl sulfate, sodium dialkyl sulfosuccinate, sodium alkyl diphenyl ether disulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate; polyoxyethylene alkyl Ether, polyoxyethylene higher alcohol ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxy Examples include nonionic surfactants such as Tylenesorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, and alkyl alkanolamide; and cationic surfactants such as alkyltrimethylammonium chloride. it can. These emulsifiers may be used alone or in combination of two or more. If necessary, a cationic surfactant such as an alkylamine hydrochloride may be used. The amount of the emulsifier is not particularly limited, but is usually 1 to 10 parts by weight based on 100 parts by weight of the monomer.

When the block copolymer (B) is produced by a suspension polymerization method, the dispersing agent to be used is not particularly limited, and for example, partially saponified polyvinyl acetate, polyvinyl alcohol, methylcellulose, carboxymethylcellulose, gelatin, Conventionally known materials such as a polyalkylene oxide, a combination of an anionic surfactant and a dispersing aid can be used. These may be used alone or in combination of two or more. The amount of the dispersant is not particularly limited, but is usually 1 to 10 parts by weight based on 100 parts by weight of the monomer.

In the production of the block copolymer (B),
The polymerization temperature is not particularly limited, but when a polymerization initiator that thermally dissociates radically is used, in terms of reaction control, the half-life in which the polymerization initiator is decomposed is just 10 hours within 50 ° C. Is preferably within 30 ° C., particularly preferably within 10 ° C.

In the production of the block copolymer (B), the oxygen concentration in the reaction system is 1000
It is preferably at most 0 ppm, more preferably at most 5,000 ppm, particularly preferably at most 1,000 ppm. For this reason, it is preferable to carry out the reaction in an atmosphere of an inert gas such as nitrogen, argon or helium.

The thermoplastic resin composition of the present invention comprises 5 to 95% by weight of the copolymer (A) and 95% by weight of the block copolymer (B).
The block copolymer (B) is preferably contained in an amount of 30% by weight or more, and more preferably 50% by weight or more, from the viewpoint that moldability, flexibility and white turbidity during deformation are suppressed. Is more preferable. The thermoplastic resin composition of the present invention may contain a vinyl polymer (C) as a component other than the copolymer (A) and the block copolymer (B). Such a vinyl polymer (C) can be obtained by polymerizing various vinyl monomers by a conventionally known method. Examples of such vinyl monomers include methyl acrylate, ethyl acrylate, N-propyl acrylate, isopropyl acrylate, n-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, toluyl acrylate, Benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, stearyl acrylate, glycidyl acrylate, 2-acryloyl Shi propyl dimethoxy methyl silane, 2-acryloyloxypropyltrimethoxysilane, acrylate trifluoromethyl, pentafluoroethyl acrylate, 2,
2,2-trifluoroethyl, 3-dimethylaminoethyl acrylate, isobutyl acrylate, 4-acrylic acid
Hydroxybutyl, t-butyl acrylate, lauryl acrylate, alkyl-modified dipentaerythritol acrylate, ethylene oxide-modified bisphenol A diacrylate, carbitol acrylate, ε-caprolactone-modified dipentaerythritol acrylate, caprolactone-modified tetrahydrofurfuryl acrylate , Caprolactone-modified neopentyl glycol hydroxypivalate diacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, tetraethylene glycol acrylate, tetrahydrofurfuryl acrylate, tripropylene glycol acrylate, tri Methylol propane ethoxy triacrylate Trimethylolpropane triacrylate, neopentyl glycol diacrylate,
Neopentyl glycol hydroxypivalate diacrylate, 1,9-nonanediol acrylate,
1,4-butanediol acrylate, 2-propenoic acid [2- [1,1-dimethyl-2-[(1-oxo-2-propenyl) oxy] ethyl] -5-ethyl-1,3- Dioxan-5-yl] methyl ester, acrylic acid esters such as 1,6-hexanediol acrylate, pentaerythritol triacrylate, 2-acryloyloxypropyl hydrogen phthalate, methyl 3-methoxyacrylate, and allyl acrylate;
Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, dimethacryl Acid tetraethylene glycol, 1,3-butylene glycol dimethacrylate, trimethylolpropane trimethacrylate, methacrylic acid n-propyl, isopropyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate, phenyl methacrylate, toluyl methacrylate, isobornyl methacrylate, methacrylic acid 2-methoxyethyl, 3-methoxybutyl methacrylate, 2-aminoethyl methacrylate, 2-methacryloyloxypropyltrimethoxysilane, 2-methacryloyloxypolypyrdimethoxymethylsilane, trifluoromethyl methacrylate, pentafluoroethyl methacrylate, Methacrylic acid esters such as 2,2,2-trifluoroethyl methacrylate; styrene, α-methylstyrene, p
Aromatic alkenyl compounds such as methylstyrene, p-methoxystyrene, divinylbenzene, and vinylnaphthalene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; conjugated diene compounds such as butadiene and isoprene; vinyl chloride, vinylidene chloride, tetra Halogen-containing unsaturated compounds such as fluoroethylene, hexafluoropropylene, vinylidene fluoride and chloroprene; silicon-containing unsaturated compounds such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, maleic acid monoester, maleic acid Unsaturated dicarboxylic acid compounds such as acid diester, fumaric acid, fumaric acid monoester, fumaric acid diester; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, cinnamic acid Vinyl ester compounds such as phenyl; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, maleimide compounds such as stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; and acrylic acid and methacrylic acid. But are not limited to these. The vinyl polymer (C) may be a homopolymer or a copolymer. The vinyl polymer (C) may be used alone or in combination of two or more. The content of the vinyl polymer (C) in the thermoplastic composition is preferably 30% by weight or less, and more preferably 10% by weight or less, in view of heat resistance and transparency.

The thermoplastic resin composition of the present invention includes:
If necessary, various additives can be blended.
Examples of such additives include fillers, coloring materials, weathering agents, ultraviolet absorbers, antioxidants, antioxidants, viscosity modifiers, water repellents, waterproofing agents, dispersants, surfactants ,solvent,
Diluents, defoamers, plasticizers, lubricants, flame retardants, pigments, tackifiers, adsorbents, compatibilizers, antistatic agents, antifouling agents, antifogging agents, hydrophilicity imparting agents, lipophilicity imparting agents , And the like.
Further, the thermoplastic resin in the present invention, terpene resin, rosin-based resin, polypropylene resin, polyethylene resin, chlorinated olefin resin, chlorinated butadiene resin,
Chlorinated isoprene resin, butyl resin, polysulfide resin, urethane resin, silicone resin, modified silicone resin, EPM resin, EPDM resin, fluorinated olefin resin, polytetrafluoroethylene resin, polyvinylidene fluoride resin, polyvinyl alcohol, etc. Can be blended.

The thermoplastic resin composition of the present invention comprises a packaging material,
It can be used as a material for medical materials, food materials, automotive materials, vibration damping materials, sealing materials, and the like. The thermoplastic resin composition of the present invention can be used for, for example, extrusion molding of sheets, films, plates, irregular shapes, and the like useful in the fields of packaging materials, architecture, civil engineering materials, automobile materials, home appliance materials, and other miscellaneous goods materials. It can be suitably used for the production of blow molded products such as products, calender molded products, bottles, etc., and various injection molded products used for automobiles and home electric appliances. In particular, it can be suitably used as a film or sheet.

When the thermoplastic resin composition of the present invention is processed into a film or a sheet, extrusion molding,
Any conventionally known molding method such as compression molding, blow molding, calender molding, vacuum molding, injection molding and the like can be applied. Among these, extrusion molding is preferred in that the production process is simple and the cost is low. Further, the film or sheet according to the present invention can be used after being molded and then stretched.

[0058]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these examples. In the following description, the gel fraction is the weight fraction of the solvent-insoluble component in the polymer, a predetermined amount of the polymer is weighed in a 100-mesh metal mesh, immersed in methyl ethyl ketone for 48 hours, and dried to obtain a residual weight. And the weight before immersion. Molecular weight,
The molecular weight distribution was determined by gel permeation chromatography (GPC). Using chloroform as an eluent, polystyrene conversion was performed using a polystyrene gel column. Glass transition temperature is JIS K7
According to the method described in 121, it was determined by differential scanning calorimetry. The tensile properties are in accordance with the method described in JIS K6251.
The average value measured three times at 0 ° C. was adopted. Regarding the change in white turbidity and transparency during deformation, the state of the fractured portion was visually observed with respect to the sample whose tensile properties were measured according to the method described in JIS K6251. Regarding the transparency, a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the total light transmittance (TT) and haze (Haze) of the film having a predetermined thickness at 23 ° C.

(Production Example 1) (Copolymer (A): Methyl methacrylate-n-butyl acrylate copolymer including a core-shell particle type graft copolymer of methyl methacrylate-n-butyl acrylate) Stirrer , A thermometer, a nitrogen gas inlet tube, a monomer addition pump, and a reflux condenser, into a 8 L reactor equipped with distilled water 4000.
g and 40 g of dioctyl sodium sulfosuccinate were charged, and the inside of the reactor was purged with nitrogen. Methyl methacrylate 90
g, 510 g of n-butyl acrylate, 0.6 g of triallyl isocyanurate, and 0.6 g of cumene hydroperoxide were placed in a reactor and heated to 40 ° C. while stirring in a nitrogen atmosphere. After 10 minutes, 0.6 g of sodium formaldehyde sulfoxylate was dissolved in 10 g of distilled water, put into a reactor, and stirred at 40 ° C. for 4 hours, and then cooled to room temperature. The thus obtained polymer (core portion) had a monomer conversion of 96% and a gel fraction of 9%.
The degree of swelling was 6%, the weight average particle diameter was 145 nm. Subsequently, the inside of the reactor was heated to 80 ° C. and stirred, and sodium formaldehyde sulfoxylate was added to 0.1 ml.
8 g was dissolved in 10 g of distilled water and added to the reactor.
Next, 200 g of methyl methacrylate, 200 g of n-butyl acrylate, and 0.6 of cumene hydroperoxide
g of the mixed solution was introduced into the reactor over 2 hours using a monomer addition pump. Stirring was further continued at 80 ° C. for 1 hour to synthesize a methyl-methacrylate-n-butyl acrylate core-shell particle type graft copolymer.

Subsequently, while heating and stirring at 80 ° C.,
800 g of methyl methacrylate, n-butyl acrylate 2
A mixed solution of 00 g and 3 g of cumene hydroperoxide was introduced into the reactor over 4 hours using a monomer addition pump. After further stirring at 80 ° C. for 1 hour, the mixture was cooled to room temperature, salted out with an aqueous solution of calcium chloride, washed with water, and dried. 1900 g of n-butyl acid copolymer was obtained.

(Production Example 2) (Block copolymer (B): methyl methacrylate-n-butyl acrylate block copolymer) 490 g of distilled water and 0.56 g of sodium dodecyl sulfate were charged into the equipped 2 L reactor, and the system was purged with nitrogen while heating and stirring at 80 ° C. 15. methyl methacrylate
A mixed solution of 5 g and 1.09 g of 2-phenylpropan-2-yldithiobenzoate was placed in a reactor,
For 20 minutes. 0.93 g of 4,4'-azobis (4-cyanovaleric acid) was put into the reactor together with 25 g of distilled water. After heating and stirring at 80 ° C. for 1 hour, 85.0 g of methyl methacrylate was put into a dropping funnel and dropped over 2 hours. Sampling was performed at the time when heating was further continued for 2 hours after completion of the dropping, and polymethyl methacrylate (conversion rate = 9)
0.1%, number average molecular weight Mn = 20100, molecular weight distribution Mw / Mn = 1.37) were confirmed.

Subsequently, 20.0 g of n-butyl acrylate was added, and 4,4′-azobis (4-cyanovaleric acid) was added.
40 g were added along with 10 g of distilled water. After heating and stirring at 80 ° C. for 1 hour, 80.0 g of n-butyl acrylate was put into a dropping funnel and dropped over 1 hour. After dropping,
After heating and stirring at 80 ° C. for 4 hours, the mixture was cooled to room temperature, salted out by adding hydrochloric acid, washed with water and dried to obtain 155 g of a methyl methacrylate-n-butyl acrylate block copolymer.
This methyl methacrylate-n-butyl acrylate block copolymer is a diblock copolymer in which the number average molecular weight of the block of the methyl methacrylate portion is 20100 and the number average molecular weight of the block of the n-butyl acrylate portion is 24200. And the molecular weight distribution Mw / Mn was 1.55. ¹ HNMR analysis confirmed that 85% of the thiocarbonylthio group was introduced into the copolymer.

(Production Example 3) (Block Copolymer (B): Methyl methacrylate-n-butyl acrylate block copolymer) 490 g of distilled water and 0.56 g of sodium dodecyl sulfate were charged into the provided 2 L reactor, and the system was purged with nitrogen while heating and stirring at 80 ° C. 15. methyl methacrylate
A mixed solution of 5 g and 1.09 g of 2-phenylpropan-2-yldithiobenzoate was placed in a reactor,
For 20 minutes. 0.93 g of 4,4'-azobis (4-cyanovaleric acid) was put into the reactor together with 25 g of distilled water. After heating and stirring at 80 ° C. for 1 hour, 85.0 g of methyl methacrylate was put into a dropping funnel and dropped over 2 hours. Sampling was performed at the time when heating was further continued for 2 hours after completion of the dropping, and polymethyl methacrylate (conversion rate = 9)
1.2%, number average molecular weight Mn = 20800, molecular weight distribution Mw / Mn = 1.35) was confirmed.

Subsequently, 20.0 g of n-butyl acrylate was added, and 4,4′-azobis (4-cyanovaleric acid) was added.
40 g were added along with 10 g of distilled water. After heating and stirring at 80 ° C. for 1 hour, 80.0 g of n-butyl acrylate was put into a dropping funnel and dropped over 1 hour. After dropping,
After heating and stirring at 80 ° C. for 4 hours, the mixture was cooled to room temperature, salted out by adding hydrochloric acid, washed with water and dried to obtain 150 g of a methyl methacrylate-n-butyl acrylate block copolymer.
This methyl methacrylate-n-butyl acrylate block copolymer is a diblock copolymer in which the number average molecular weight of the block of the methyl methacrylate portion is 20800 and the number average molecular weight of the block of the n-butyl acrylate portion is 25300. And the molecular weight distribution Mw / Mn was 1.67. ¹ HNMR analysis confirmed that 88% of the thiocarbonylthio group was introduced into the copolymer.

140 g of this diblock copolymer was dissolved in 1000 mL of toluene and placed in a 2 L reactor equipped with a stirrer, thermometer, nitrogen gas inlet tube and reflux condenser, and the system was purged with nitrogen. To this, 9.8 g of diethylamine was added, and the mixture was heated at 80 ° C. for 5 hours.
The thiocarbonylthio group attached to the -butyl end was quantitatively converted to a mercapto group. Subsequently, 0.22 g of hexamethylene diisocyanate and 0.03 g of dibutyltin bisisooctylthioglycolate were added, and the mixture was added at 80 ° C. for 2 hours.
By heating at 100 ° C. for 3 hours, a triblock copolymer of methyl methacrylate-n-butyl acrylate-methyl methacrylate was obtained with a yield of 80%.

(Production Example 4) (Copolymer (B): Methyl methacrylate-n-butyl acrylate block copolymer) A stirrer, a thermometer, a nitrogen gas inlet tube, a dropping funnel, and a reflux condenser were provided. 500 L of toluene, 100 g of methyl methacrylate, and 3.19 g of S, S-di (1-phenylethyl) trithiocarbonate were placed in a 2 L reactor.
It was replaced with nitrogen. Here, azobisisobutyronitrile 0.1.
82 g was added and the mixture was heated and stirred at 60 ° C. for 20 hours. Upon sampling and analysis, the number average molecular weight Mn was 96.
00, formation of polymethyl methacrylate having a molecular weight distribution of Mw / Mn = 1.32 was confirmed. From 1H NMR analysis, it was confirmed that a trithiocarbonate group was introduced into the polymer main chain at a ratio of 84%.

Subsequently, 0.25 g of azobisisobutyronitrile was added into the reactor, and 400 g of n-butyl acrylate was added from a dropping funnel while heating and stirring at 60 ° C.
It was dropped over time. After completion of the dropwise addition, heating and stirring were continued for another 10 hours, and the mixture was cooled to room temperature. Methanol 3
The mixture was poured slowly into L with stirring to precipitate the copolymer. The precipitate was filtered, washed with ethanol and dried, yielding 750 g as a powder. As a result of the analysis, it was a triblock copolymer of methyl methacrylate-n-butyl acrylate-methyl methacrylate, and a number average molecular weight Mn =
39500, it was confirmed that the molecular weight distribution was Mw / Mn = 1.71. ¹ H NMR analysis also confirmed the presence of a trithiocarbonate group.

(Production Example 5) (Methyl methacrylate-n-butyl acrylate copolymer) A methyl methacrylate-n-butyl acrylate copolymer was added without adding a chain transfer agent having a thiocarbonylthio structure. Synthesis of the coalescence was performed. 490 g of distilled water and 0.55 g of sodium dodecyl sulfate were placed in a 2 L reactor equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a dropping funnel, and a reflux condenser. did. 16.4 g of methyl methacrylate was placed in a reactor,
For 20 minutes. 0.93 g of 4,4'-azobis (4-cyanovaleric acid) was put into the reactor together with 25 g of distilled water. After heating and stirring at 80 ° C. for 1 hour, 85.0 g of methyl methacrylate was put into a dropping funnel and dropped over 2 hours. Sampling was performed at the time when heating was further continued for 2 hours after completion of the dropping, and polymethyl methacrylate (conversion rate = 9)
6.5%, number average molecular weight Mn = 21400, molecular weight distribution Mw / Mn = 2.11) was confirmed to be formed.

Subsequently, 20.0 g of n-butyl acrylate was added, and 4,4′-azobis (4-cyanovaleric acid) was added.
41 g were added along with 10 g of distilled water. After heating and stirring at 80 ° C. for 1 hour, 80.0 g of n-butyl acrylate was put into a dropping funnel and dropped over 1 hour. After dropping,
After heating and stirring at 80 ° C. for 2 hours, the mixture was cooled to room temperature, salted out by adding hydrochloric acid, washed with water and dried to obtain 180 g of a methyl methacrylate-n-butyl acrylate copolymer. This methyl methacrylate-n-butyl acrylate copolymer,
The number average molecular weight of the methyl methacrylate moiety is 21400,
The number average molecular weight of the n-butyl acrylate moiety is 3160
0 and a molecular weight distribution Mw / Mn = 2.98
Met. However, homopolymers of polymethyl methacrylate and poly-n-butyl acrylate were partially contained, respectively.

Example 1 65 parts by weight of a methyl methacrylate-n-butyl acrylate copolymer produced in Production Example 1 and a methyl methacrylate-n-butyl acrylate diblock copolymer produced in Production Example 2 35 parts by weight and 0.2 parts by weight of Irganox 1010 (manufactured by Ciba-Geigy) as a stabilizer were mixed and roll-kneaded at 200 ° C. for 5 minutes. This part was press-formed at 200 ° C. to obtain a flexible and transparent sheet having a thickness of 2 mm. Tensile properties at 0 ° C. are elastic modulus of 202 MPa and breaking strength of 13 M
Pa and elongation at break were 112%. No cloudiness or change in transparency was observed in the fracture surface after the tensile test.
A part of the roll kneaded material was press-formed at 200 ° C. to form a 250 μm thick film, and the transparency was evaluated. TT = 90%, Haze = 8%.

Example 2 67 parts by weight of a methyl methacrylate-n-butyl acrylate copolymer produced in Production Example 1 and methyl methacrylate-n-butyl acrylate-methyl methacrylate produced in Production Example 3 33 parts by weight of a block copolymer, Irganox 1010 as a stabilizer
(Ciba Geigy Co., Ltd.) 0.2 parts by weight, and kneaded with a roll at 200 ° C. for 5 minutes. Part of this is 20
Press forming was performed at 0 ° C. to obtain a flexible and transparent sheet having a thickness of 2 mm. Tensile properties at 0 ° C. have an elastic modulus of 235.
MPa, breaking strength was 20 MPa, and elongation at break was 85%. No cloudiness or change in transparency was observed in the fracture surface after the tensile test. In addition, a part of the roll kneaded material is 200
The film was press-formed at a temperature of ° C. to form a film having a thickness of 203 micrometers, and the transparency was evaluated. TT = 92%, Haz
e = 5%.

Example 3 67 parts by weight of a methyl methacrylate-n-butyl acrylate copolymer produced in Production Example 1 and methyl methacrylate-n-butyl acrylate-methyl methacrylate produced in Production Example 4 33 parts by weight of a block copolymer, Irganox 1010 as a stabilizer
(Ciba Geigy Co., Ltd.) 0.2 parts by weight, and kneaded with a roll at 200 ° C. for 5 minutes. Part of this is 20
Press forming was performed at 0 ° C. to obtain a flexible and transparent sheet having a thickness of 2 mm. Tensile properties at 0 ° C. have an elastic modulus of 250
The breaking strength was 18 MPa, and the elongation at break was 83%. No cloudiness or change in transparency was observed in the fracture surface after the tensile test. In addition, a part of the roll kneaded material is 200
The film was press-formed at a temperature of 200 ° C. to form a film having a thickness of 220 μm, and the transparency was evaluated. TT = 91%, Haz
e = 5%.

(Example 4) 33 parts by weight of the methyl methacrylate-n-butyl acrylate copolymer produced in Production Example 1 and methyl methacrylate-n-butyl acrylate-methyl methacrylate produced in Production Example 3 67 parts by weight of a block copolymer, Irganox 1010 as a stabilizer
(Ciba Geigy Co., Ltd.) 0.2 parts by weight, and kneaded with a roll at 200 ° C. for 5 minutes. Part of this is 20
Press forming was performed at 0 ° C. to obtain a flexible and transparent sheet having a thickness of 2 mm. Tensile properties at 0 ° C have an elastic modulus of 15M
Pa, the breaking strength was 11 MPa, and the elongation at break was 189%. No cloudiness or change in transparency was observed in the fracture surface after the tensile test. In addition, a part of the roll kneaded material is 200
The film was press-formed at a temperature of ° C. to form a film having a thickness of 185 μm, and the transparency was evaluated. TT = 92%, Haz
e = 9%.

Example 5 33 parts by weight of the methyl methacrylate-n-butyl acrylate copolymer produced in Production Example 1, the methyl methacrylate-n-butyl acrylate-methyl methacrylate produced in Production Example 4 67 parts by weight of a block copolymer, Irganox 1010 as a stabilizer
(Ciba Geigy Co., Ltd.) 0.2 parts by weight, and kneaded with a roll at 200 ° C. for 5 minutes. Part of this is 20
Press forming was performed at 0 ° C. to obtain a flexible and transparent sheet having a thickness of 2 mm. Tensile properties at 0 ° C have an elastic modulus of 14M
Pa, the breaking strength was 15 MPa, and the elongation at break was 165%. No cloudiness or change in transparency was observed in the fracture surface after the tensile test. In addition, a part of the roll kneaded material is 200
The film was press-formed at a temperature of 200 ° C. to form a film having a thickness of 200 μm, and the transparency was evaluated. TT = 90%, Haz
e = 9%.

Comparative Example 1 100 parts by weight of the methyl methacrylate-n-butyl acrylate copolymer produced in Production Example 1 and 0.2 parts by weight of Irganox 1010 (manufactured by Ciba Geigy) as a stabilizer. 200 ℃
For 5 minutes. A part of this was pressed at 200 ° C. to obtain a transparent sheet having a thickness of 2 mm. 0
Tensile properties at 6 ° C. are elastic modulus 685 MPa, breaking strength 3
It was 0 MPa and elongation at break was 31%. The fracture surface after the tensile test was white and cloudy. Also, a part of the roll kneaded material is
Press molding was performed at 0 ° C. to form a film having a thickness of 234 μm, and the transparency was evaluated. TT = 94%, Ha
ze = 5%.

Comparative Example 2 Methyl methacrylate-n-butyl acrylate copolymer prepared in Production Example 1 67 parts by weight, methyl methacrylate-n-butyl acrylate diblock copolymer prepared in Production Example 5 33 parts by weight and 0.2 parts by weight of Irganox 1010 (manufactured by Ciba Geigy) as a stabilizer were mixed and roll-kneaded at 200 ° C. for 5 minutes. A part of this was press-formed at 200 ° C. to obtain a soft but slightly white turbid sheet having a thickness of 2 mm. The tensile properties at 0 ° C. were an elastic modulus of 204 MPa, a breaking strength of 12 MPa, and an elongation at break of 90%. In the fracture surface after the tensile test, it was confirmed that the transparency was slightly lowered. A part of the roll kneaded material was press-formed at 200 ° C. to form a film having a thickness of 204 micrometers.
The transparency was evaluated. TT = 72%, Haze = 19%
Met.

[0077]

The film or sheet formed from the thermoplastic resin composition of the present invention has excellent flexibility and does not become clouded or change in transparency even when deformed at a low temperature.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 53/00 C08L 53/00 F term (reference) 4F071 AA33 AA75 AA76 AA77 BB04 BC01 4J002 BG04W BG04Y BG05W BG05Y BG07W BN12W BP03X GG02 GQ00 4J026 AA45 AC09 BA27 BA28 BA32.

Claims (8)

[Claims] 1. A block copolymer containing 5-95% by weight of a copolymer (A) composed of an acrylate ester and a methacrylate ester, and a methacrylate ester-based polymer block and an acrylate ester-based polymer block. (B) a thermoplastic resin composition comprising 95 to 5% by weight, and a block copolymer (B) produced by radical polymerization using a compound having a thiocarbonylthio structure as a chain transfer agent. Characterized in that:
Thermoplastic resin composition. 2. The thermoplastic resin composition according to claim 1, wherein the copolymer (A) is a copolymer composed of butyl acrylate and methyl methacrylate. 3. A polymer block containing at least 80% by weight of methyl methacrylate, wherein the block copolymer (B) comprises:
3. The thermoplastic resin composition according to claim 1, further comprising a polymer block containing butyl acrylate in an amount of 80% by weight or more. 4. The copolymer (A) contains at least 50% by weight of a core-shell particle type graft copolymer (A-1) obtained by graft-polymerizing an outer layer portion called a shell on an inner layer portion called a core. The thermoplastic resin composition according to any one of claims 1 to 3, characterized in that: 5. The thermoplastic resin composition according to claim 4, wherein the copolymer (A) contains at least 90% by weight of the core-shell particle type graft copolymer (A-1). 6. A core-shell particle type graft copolymer (A)
The thermoplastic resin composition according to claim 4 or 5, wherein the weight average particle diameter of the core portion in -1) is in the range of 30 to 200 nanometers. 7. The composition according to claim 1, further comprising a vinyl polymer (C) as a component other than the copolymer (A) and the block copolymer (B). Thermoplastic resin composition. 8. A film or sheet formed from the thermoplastic resin composition according to claim 1.